US4131574A - Starch - Google Patents

Starch Download PDF

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Publication number
US4131574A
US4131574A US05/813,556 US81355677A US4131574A US 4131574 A US4131574 A US 4131574A US 81355677 A US81355677 A US 81355677A US 4131574 A US4131574 A US 4131574A
Authority
US
United States
Prior art keywords
starch
slurry
resin
solution
formaldehyde
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/813,556
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English (en)
Inventor
Harold Isherwood
John T. Shaw
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
British Industrial Plastics Ltd
Original Assignee
British Industrial Plastics Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by British Industrial Plastics Ltd filed Critical British Industrial Plastics Ltd
Application granted granted Critical
Publication of US4131574A publication Critical patent/US4131574A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/28Starch
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04Starch derivatives, e.g. crosslinked derivatives
    • C08L3/10Oxidised starch

Definitions

  • This invention relates to starch and, in particular, to a thermochemically converted starch.
  • starch In the manufacture of paper starch is used for various purposes including sizing, to improve surface quality, to improve the quality on subsequent coating. It is also added to the body of the paper to improve internal bonding, for stiffening as in the manufacture of corrugated paper products. Starch is also used in glues for subsequent paper treatments.
  • Raw starch can be swollen and obtained as a colloidal aqueous solution but for use in commercial processing the viscosity of the solution at low solids contents is too high for acceptable concentrations to be used and the stability of the solution is poor.
  • Thermomechanical conversion involves subjecting a starch slurry to a high temperature and mechanical shear, e.g. by injection of live steam at high pressure. This method can produce an acceptable viscosity starch solution at 8% solids content but its stability is not good.
  • Thermochemical conversion of the starch involves adding, for example, oxidising agent to the starch slurry which is treated in a similar way as in thermomechanical conversion. This method enables acceptable viscosities to be obtained at higher starch concentrations but the stability of them is not good.
  • starch solution The stability of the starch solution is its ability to retain a low viscosity during storage. Both converted and raw starches form solutions which have a tendency to increase irreversibly in viscosity as they cool e.g. to below 50° C. so that subsequent heating of the solution does not restore its original viscosity. This phenomenon is usually referred to as starch "set-back" in the industry.
  • the present invention provides a method for the manufacture of starch solution which comprises the steps of forming a slurry of substantially raw starch in water, adding to said slurry an amino formaldehyde resin, and oxidising agent, and subjecting said slurry to mechanical shear at a temperature in the range 110° C. to 180° C.
  • thermochemical conversion may be carried out on a starch which is not completely raw, i.e. on which some partial conversion has already been carried out. With such starches the method of the invention can still be used although the advantages thereby obtained may not be wholly the same as with completely raw starch.
  • the invention also provides a starch solution comprising a starch and amino-formaldehyde resin manufactured by the method described above.
  • the amino-formaldehyde resin is preferably urea-formaldehyde resin of known type, with a low degree of condensation, i.e. a resin with good water dilutability and preferably also a low level of free formaldehyde e.g. not more than 1.5% on weight of resin.
  • the ratio of urea to formaldehyde is preferably in the range 1:1.1 up to 1:2.5.
  • the oxidising agent is preferably hydrogen peroxide although other oxidising agents such as Sodium or Potassium persulphate may also be used.
  • a catalyst is generally used to promote reaction of the oxidising agent with the starch, a particularly suitable catalyst being Copper Sulphate (Cu SO 4 5H 2 O).
  • the amount of catalyst used is small e.g. 50 to 250 ppm (on dry starch) and is usually added direct to the starch slurry.
  • the slurry is preferably subjected to mechanical shear at an elevated temperature by means of injection of live steam into the slurry at sufficiently high pressure to obtain reaction temperature, in a thermochemical starch converter, which may be of any of the known types.
  • a thermochemical starch converter which may be of any of the known types.
  • the pressure in the converting head may be 2 to 6 Kgf/cm 2 .
  • an alkali may be added to the starch solution after subjection to shear and temperature to adjust the pH of the solution, and also other additives may be added where required.
  • the amount of resin added to the starch slurry may be up to 30% by weight of the total weight of dry starch in the slurry.
  • the actual amount used will generally be less than 30%, for example in the range 2% to 15% and is dependent also upon the efficiency of the converter.
  • the amount of oxidising agent used may be the same as in a conventional thermochemical starch conversion. It will generally be in the approximate range 1 to 3 percent by weight of oxidising agent based on the weight of starch solids but the actual amount is varied according to the actual converter. If the oxidising agent and resin are simply added to a slurry of starch, the resulting slurry is liable to react before it has all been passed to the converter and so not be convertible. It is therefore preferred to add at least either the oxidising agent or the resin to the slurry only as it is passing to the converter i.e. immediately before it is to be subjected to heat and shear. More preferably both resin and oxidising agent are so treated and added individually as the slurry is passing to the converter.
  • Starch solutions prepared by the method of this invention may be used to improve the properties of paper in the usual way.
  • the solutions may be employed in treatment of the paper during manufacture e.g. by application at the size press on a conventional paper-making machine.
  • the slurry was passed through a thermochemical converter at a rate of 2600 liters/hour, together with dilution water (745 liters/hour), and aqueous Hydrogen peroxide solution of 3.5% concentration (wt/vol) (80 liters/hour).
  • Live steam was injected into the slurry in the converter, the pressure in the converter being 4-5 Kgf/cm 2 , and the dwell time of starch in the converter, i.e. the time during which the starch was subject to conversion conditions during its passage through the converter, was approx. 50 seconds.
  • the final starch solution has a solids content of 15% of which 13.8% was starch and 1.2% resin.
  • the viscosity of the solution at 78° C. was 26 cp.
  • thermochemically converted starch has been previously proposed, but only after the thermochemical conversion, when it was found that the stability of the starch solution was reduced. Since the resin is a polyfunctional compound it may be expected that when the resin is added before thermochemical conversion of the starch co-reaction with the starch would result in a higher viscosity in the final product. In practice we have now found that only minor viscosity difference from thermochemically converted starch solution not containing the resin occurs whilst significant improvement in resistance to viscosity change on storage is obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
US05/813,556 1976-07-09 1977-07-07 Starch Expired - Lifetime US4131574A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB28588/76 1976-07-09
GB2858876 1976-07-09

Publications (1)

Publication Number Publication Date
US4131574A true US4131574A (en) 1978-12-26

Family

ID=10277983

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/813,556 Expired - Lifetime US4131574A (en) 1976-07-09 1977-07-07 Starch

Country Status (12)

Country Link
US (1) US4131574A (ja)
JP (1) JPS539334A (ja)
AU (1) AU2678877A (ja)
BE (1) BE856654A (ja)
DE (1) DE2731006A1 (ja)
FI (1) FI772123A (ja)
FR (1) FR2357576A1 (ja)
IL (1) IL52434A (ja)
NL (1) NL7707373A (ja)
NO (1) NO143384C (ja)
SE (1) SE7708002L (ja)
ZA (1) ZA774027B (ja)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023104A1 (en) * 1995-01-24 1996-08-01 National Starch And Chemical Investment Holding Corporation Paper containing thermally-inhibited starches
US5641349A (en) * 1995-01-24 1997-06-24 National Starch And Chemical Investment Holding Corporation Water-based adhesives containing thermally-inhibited starches
US5718770A (en) * 1994-08-25 1998-02-17 National Starch And Chemical Investment Holding Corporation Thermally-inhibited pregelatinized granular starches and flours and process for their production
US5720822A (en) * 1995-06-07 1998-02-24 National Starch And Chemical Investment Holding Corporation Thermally-inhibited pregelatinized non-granular starches and flours and process for their production
US5830884A (en) * 1995-01-18 1998-11-03 National Starch And Chemical Investment Holding Corporation Pharmaceutical products containing thermally-inhibited starches
US5871756A (en) * 1995-01-18 1999-02-16 National Starch And Chemical Investment Holding Corporation Cosmetics containing thermally-inhibited starches
US5932017A (en) * 1993-07-30 1999-08-03 National Starch And Chemical Investment Holding Corporation Thermally-inhibited non-pregelatinized granular starches and flours and process for their preparation
US6090884A (en) * 1998-05-07 2000-07-18 S. C. Johnson Commercial Markets, Inc. Starch degradation/graft polymerization composition, process, and uses thereof
US6221420B1 (en) 1993-07-30 2001-04-24 National Starch And Chemical Investment Holding Corporation Foods containing thermally-inhibited starches and flours
US9982064B2 (en) 2012-10-02 2018-05-29 Tate & Lyle Ingredients Americas Llc Process for preparing an inhibited starch

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1112287B1 (en) * 1998-09-11 2002-06-05 Coöperatieve Verkoop- en Productievereniging van Aardappelmeel en Derivaten 'AVEBE' B.A. Oxidation of starch

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2317752A (en) * 1939-10-30 1943-04-27 Nat Starch Products Inc Modified starch
US2450377A (en) * 1944-07-31 1948-09-28 Penick & Ford Ltd Inc Starch-resin reaction product and method of producing the same
US3211564A (en) * 1961-06-13 1965-10-12 Kimberly Clark Co Continuous high temperature process for oxidized starch for coating compositions
US3255040A (en) * 1964-01-13 1966-06-07 Union Starch & Refining Co Inc Process of making coating color starch pastes and starch pastes so produced
US3475215A (en) * 1967-03-14 1969-10-28 West Virginia Pulp & Paper Co Continuous process for the simultaneous acid hydrolysis and oxidation of starch for use in coating compositions
US3539366A (en) * 1968-09-10 1970-11-10 Standard Brands Inc Starch process
US3836376A (en) * 1970-08-11 1974-09-17 Ogilvie Flour Mills Co Ltd Starch-based adhesive compositions
US3973985A (en) * 1974-06-03 1976-08-10 Anheuser-Busch, Incorporated Starch product by further oxidizing oxidized starch with ammonium persulfate
US4040862A (en) * 1976-07-02 1977-08-09 Anheuser-Busch, Incorporated Process for making a thermal converting starch by modification of oxidized starch with aluminum salts

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629166A (en) * 1968-07-26 1971-12-21 Nippon Pulp Industry Co Ltd Coating color a coated paper applied with said coating color and a process for preparing said coated paper
US3869296A (en) * 1972-03-29 1975-03-04 Union Carbide Corp Aqueous starch-pigment paper coating compositions containing glyoxal-urea insolubilizer
USB408030I5 (ja) * 1973-10-19 1975-01-28

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2317752A (en) * 1939-10-30 1943-04-27 Nat Starch Products Inc Modified starch
US2450377A (en) * 1944-07-31 1948-09-28 Penick & Ford Ltd Inc Starch-resin reaction product and method of producing the same
US3211564A (en) * 1961-06-13 1965-10-12 Kimberly Clark Co Continuous high temperature process for oxidized starch for coating compositions
US3255040A (en) * 1964-01-13 1966-06-07 Union Starch & Refining Co Inc Process of making coating color starch pastes and starch pastes so produced
US3475215A (en) * 1967-03-14 1969-10-28 West Virginia Pulp & Paper Co Continuous process for the simultaneous acid hydrolysis and oxidation of starch for use in coating compositions
US3539366A (en) * 1968-09-10 1970-11-10 Standard Brands Inc Starch process
US3836376A (en) * 1970-08-11 1974-09-17 Ogilvie Flour Mills Co Ltd Starch-based adhesive compositions
US3973985A (en) * 1974-06-03 1976-08-10 Anheuser-Busch, Incorporated Starch product by further oxidizing oxidized starch with ammonium persulfate
US4040862A (en) * 1976-07-02 1977-08-09 Anheuser-Busch, Incorporated Process for making a thermal converting starch by modification of oxidized starch with aluminum salts

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932017A (en) * 1993-07-30 1999-08-03 National Starch And Chemical Investment Holding Corporation Thermally-inhibited non-pregelatinized granular starches and flours and process for their preparation
US6221420B1 (en) 1993-07-30 2001-04-24 National Starch And Chemical Investment Holding Corporation Foods containing thermally-inhibited starches and flours
US5718770A (en) * 1994-08-25 1998-02-17 National Starch And Chemical Investment Holding Corporation Thermally-inhibited pregelatinized granular starches and flours and process for their production
US5830884A (en) * 1995-01-18 1998-11-03 National Starch And Chemical Investment Holding Corporation Pharmaceutical products containing thermally-inhibited starches
US5871756A (en) * 1995-01-18 1999-02-16 National Starch And Chemical Investment Holding Corporation Cosmetics containing thermally-inhibited starches
WO1996023104A1 (en) * 1995-01-24 1996-08-01 National Starch And Chemical Investment Holding Corporation Paper containing thermally-inhibited starches
US5641349A (en) * 1995-01-24 1997-06-24 National Starch And Chemical Investment Holding Corporation Water-based adhesives containing thermally-inhibited starches
US5720822A (en) * 1995-06-07 1998-02-24 National Starch And Chemical Investment Holding Corporation Thermally-inhibited pregelatinized non-granular starches and flours and process for their production
US6261376B1 (en) 1995-06-07 2001-07-17 National Starch And Chemical Investment Holding Corporation Thermally-Inhibited pregelatinized non-granular starches and flours
US6090884A (en) * 1998-05-07 2000-07-18 S. C. Johnson Commercial Markets, Inc. Starch degradation/graft polymerization composition, process, and uses thereof
US9982064B2 (en) 2012-10-02 2018-05-29 Tate & Lyle Ingredients Americas Llc Process for preparing an inhibited starch

Also Published As

Publication number Publication date
BE856654A (fr) 1978-01-09
IL52434A (en) 1980-06-30
FI772123A (ja) 1978-01-10
FR2357576A1 (fr) 1978-02-03
NL7707373A (nl) 1978-01-11
JPS539334A (en) 1978-01-27
SE7708002L (sv) 1978-01-10
FR2357576B1 (ja) 1980-04-25
NO143384C (no) 1981-01-28
NO772421L (no) 1978-01-10
IL52434A0 (en) 1977-10-31
NO143384B (no) 1980-10-20
DE2731006A1 (de) 1978-01-12
ZA774027B (en) 1978-05-30
AU2678877A (en) 1979-01-11

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